N-substituted urea and carbamate derivatives of water-insoluble tertiary amines



United States Patent Ofifice.

N-SUBSTITUTED UREA AND CARBAMATE DE- RIVATIg'ES F WATER-INSOLUBLE TERTIARY Ernest Merian, Bottmingen, Bruno J. R. Nicolaus, Basel, Switzerland, assignors to Sandoz A.G., Basel, Switzerland, a Swiss firm No Drawing. Application July 12, 1957 Serial N0. 671,409

Claims priority, application Switzerland July 18, 1956 7 Claims. Cl. 260-472) The present invention relates to a process for the production of new water-insoluble tertiary amines of the general formula:

wherein r 2,909,561 Patented Oct. 20, 1959 2 tertiary amines consists in reacting 1 mol of a compound of the formula i1 (II) wherein Y x, y, n, Z, R and R have the meanings recited in the foregoing,

Q stands for hydrogen, halogen, the hydroxy, amino, methoxy, ethoxy, difluoromethyl or trifluoromethyl, carbalkoxy or cyano group, when n has the value 1,

' and for a single carbon-nitrogen linkage, when n has the value 2,

l with 1 or 2 moles of an isocyanate of the formula x denotes hydrogen, halogen or a low molecular alkyl or 7 alkoxy radical,

y hydrogen, halogen, a low molecular alkyl or alkony radical or the trifluoromethyl or trifluoroacetyl radical or an alkanoylamino radicalwith not more than 18 carbon atoms, n the number 1 or 2, V R an alkylene radical with 1 to 4 carbon atoms, R an alkylene radical with 2 to 4'carbon atoms,

R an aliphatic, cycloaliphatic or aromatic radical which is free from sulfur and may contain fuither'substituents,

vZ oxygen or the imino group, and

M hydrogen, halogen, the methoxy, ethoxy, cyano, di-

tfluoromethyl, trifluoromethyl or carbalkoxy radical, or'

in which R and Z possessthe aforementioned mean ings, when n has the value 1, or a single carbon-nitrogen linkage, when n has the value 2.

Especially valuable water-insoluble tertiary amines are those which correspond to the Formula I wherein n and Z have the aforenamed meanings and x denotes hydrogen or a low molecular alkyl or alkoxy radical,

y denotes hydrogen or a low molecular alkyl or alkoxy p, R denotes a methylene or ethylene radical, R denotes an ethylene or Z-methylethylene radical,

R denotes a low molecular alkyl radical, the cyclohex yl radical or a phenyl radical which may be'arfnonionic substituents, and f A, M denotes hydrogen, halogen, the cyano, the trifluoromethyl or a -Z-CONH R group, in which Z and R have the above stated significances, when n has the value 1, and the singlecarbon-nitrogen linkage, when.

n has the value 2;

Throughout the specification the terms lower,allyl and lower alkoxy stand for alkyl andf" al ko ry; re?

spectively containing 1 to 6 carbon atoms.

The process for the production of the water-insoluble wherein R has one of the above-stated meanings.

The reaction of the compounds of Formula H with the isocyanates is carried out advantageously in solution (e.g. in an indifferent organic solvent) or, when liquid or liquefied components are employed, by direct mixing. The reaction temperature may vary within wide limits in accordance with the operating procedure that is adopted. The new products are isolated by one of the common basic operations, e.g. filtration, evaporation of the solvent or precipitation from the solvent with a suitable agent.

The new compounds are valuable intermediate prod- (III) ucts which find employment in the manufacture of dyestulfs and pharmaceutical products. Thus, upon coupling the initially mentioned tertiary amines of Formula I with diazo compounds, which latter may contain further substituents commonly used in 2120 dyestuffs but are free from water-solubilizing groups, one arrives at water-insoluble az'o dyestufi's having the formula Alternatively an aldehyde group can be introduced into the compounds of Formula I in the para-position to the tertiary amino group, using the known methods. These aldehydes can be condensed with compounds con- 1 taining active methylene groups to give styryl dyestuffs which correspond to the formula:

wherein 1 x,y1n, R R R3, M and Z have the initially mentioned meanings and A denotes the radical of an open chain or cyclic com- 'pound containing active methylene groups, which radical is condensed on the active methylene group and may contain 'further subs'tituents except water- "solubilizing groups, e.g. the radical of malonic acid dinitrile or that of a cyanoacetic acid ester, a benzenesulfoacetonitrile or 1.3.3-trimethyl-Z-methyleneindoline.

The water-insoluble azo and styryl dyestufis obtained and are characterized by the symbols y and R columns I and II and by the shade in acetone solution of the coupling products with 4-nitrobenzene-l-diazonium chloride (column III).

thus are suitable for dyeing cellulose ester fibers from 5 Table 2 aqueous dispersion and in the spinning solution. They have similar suitability for dyeing synthetic polyarnide, polyvinyl and terephthalic acid ester fibers, on Which f (I) (In) they give dyeings characterized by excellent fastness y properties. 8 M th 1 In the examples which follow the parts and percentages 10 9111 mil flffj ia gj are by weight; the temperatures are in degrees centigrade i %ggf 33- and the melting points are uncorrected. $1: nuor'55tt'y'1I..-" Yellow orange.

D EXAMPLE 1 14" Brniiiiii: D3.

15 Aeetylarnino Scarlet-red. 89.5 parts of 1-(N-ethyl-N-B-hydroxyethyl)-ammo-3- 15 g li i l l -a ty Scarlet. methylbenzene, 100 parts of dry benzene and 43 parts of fij: ethylisocyanate are mixed and boiled with reflux. After Do Yellow orange. Orange. Do.

some time the mixture is concentrated by evaporation and then distilled in a high vacuum. At a pressure of 0.03 mm. and 130-132 the eth-ylcarbaminic acid ester 32;; ggg of the 1-(N-ethyl-N-B-hydroxyethyl)-am1no-3-methylben 3g" g m Bo. zene distils over. It has a melting point at and is flgfifig obtained in a good yield 28-. Trifluoro-acetylamino scarlet.

Yellow-orange. EXAMPLE 2 oraljitgg. Do:

89.5 parts of 1-(N-ethyl-N-B-hydroxyethyl)-amino-3- methylbenzene and 72 parts of phenylisocyanate are mixed and gently heated. After some time the reaction is completed and the congealed product is re-crystallized Yellow-orange.

D0. Scarlet-red. Scarlet. Orange.

from benzeneor ethyl alcohol. A good yield of the phenylcarbarninic acid. ester of the l-(N-ethyl-N-fi-hyga flupro e y e -o edroxyethyl)-amino-3-methylbenzene is obtained. Its g: 33;; B2: melting point is 88-90. 43.. Acetylamino Scarlet-red.

3%-. gnguoro-acetylam o Scarlet.

Y 11 EXAMPLE 3 35 46 "E4392?" 4j-ethylphenyln e lgvgomnge 184 parts of 1-(N-fl-cyanoethyl-N-fl-hydroxyethyb- 4ftert-butylphenyLm 3-methylphcnyl Do. ammo-methylbenzene, 200 parts of benzene and 84 d 3:-met hoxyphenyl Do. parts of ethylisocyanate are boiled for 48 hours with ggfg g g g O reflux, after which the benzene is distilled off at in d I z meifi ififiefi ifiiii I s: vacuo. The waxlike residue which remains is the iigggggfiififg g3: ethylcarbarnlmc acld ester of the l-(N-fi-cyanoethyl-N-fl- 4-tert.-amylpheny Do. hydroxyethyl)-amino-3-methylbenzene, which melts at 32' about Do:

In Table I below valuable tertiary amines are enumerg3 Ethoxy B8 Yellow-orange.

ated which can be produced by the process described in 5 61 Ohlnrinp D 62 Bromine the foregoing. They correspond to the general formula 63 x 64 Tr1fiu0r-acetylammo Scarlet. I R5 65 Acetylamrno Scarlet-red.

In Table 3 further valuable water-insoluble tertiary amines are described. They correspond to the formula The meanings of x, y, R R R and Z are given in R5 columns I to VI respectively. Column VII contains the melting points of the new compounds and column VIII 55 the shade in acetone solution of the coupling products P a with 4-nitrobenzene-1-diazonium chloride. 7 (VIII) Ex. (I) (II) (III) (IV (VII) VI No. I y R5 R2) 21 (2D M.P. H)

H Methyl..- Cyanoethyl Ethylene- Ethyl-.- Oxygen... 98 Scarlet-red. H d phenyL. ,110 Scarlet. H do 97 Orange. H do Scarlet.

Table 2 contains further valuable tertiary amines which can be produced according to the present process. They. V have the general formula and are characterized by the symbols x, y, w, R and R 0133 in columns I to V and by the shade in acetone solution of the coupling. products with v4-nitrobenzene-1-diazonium 75 chlorlde in column VI. (VII) mi Y m Table s l 1; 2

Ex. (I) (n) (In) (Iv) 1 V (V) (W) No. a: l y w x R: RI

Hydrogen. Hydrogen. Hydrogen. Yellow-orange. Chlorlne" do do Yellow.

Bromine.. -do 7 Orange. Do. Isopropyl- Do. Methoxy do Do. Ethoxy--- do Do. Chlorine. Methyl Do. Bromine" do 7 D0.

Red.

Do. Do. Do. Do. Methyl.-- Methoxy. Do. do Methyl Do. 0 do Do.

Hydrogem do Orange-red. do Hydrogen. Orange. .-do do Orange-red.

Do. Orange. 0. Red.

0. Orange. Do. yl Do. (2-earbomethoxy)-ethyl. Do. (2-earbethoxy)-ethy1. Do. 2'-ehloroethyl Orange-red. '2-bromoethyl. Do.

2-methoxyethy1 Red. 2-ethoxyethy1 D0.

0 yl Scarlet-red. Scarlet. 2..2.2'-trlfluoroethyl Orange-red. (2"carbomethoxy)-ethyl D0. Ethyl Red.

dn 4-methyl- Do. phenyl.

do n-Bntyl Do. do Ethyl 0 Do. (1 d H 1 em (in o range-re jl o g rln n-Buty Do. (in dn (2-oarbomethoity)-ethyl. 4-methyl- Do.

- phenyl. 112 dn dn rln fin PhenyL Scarlet. 113---- Methyl-" Methyl ,dn do d {Red 114 .do Methoxy on o Table 4 contains some water-insoluble tertiary amines 1 In the following Table 5 are listed a few tertiary amines of the general formula of the formula 1U 11 CO NH R3 v 1/ (X) l w y are characterized y the y x, J 5 and amples 1 to 3. They are characterized by the symbols R in columns I to V and by the shade of the acetone w nd R in c lumns I to IV and b the shade in Solution of the cflllpling Products W 4-I1itr0be11ZeI1e-1- acetone solution of the coupling products with 4-nitrodiazonium chloride in column VI. be'nzene-l-diazonium chloride in column V.

? Table-4 Ex. (I) (II) (III) (IV) (V) 1 VI No. x 1 "w v Rs Rx Hydrogen. Hydrogen- Ethyl Ethyl Scarlet. do (do n-Butyl n Do. ,7 do do do 4 methylphenyl -Do. .do do do Phenyl Do. i Methyl-.. do do Ethyl Red. J do do do n-Butyl 1 Do. -do do do 4-methylphenyl 7 Do. d do do Phenyl V 0.

Hydrogen. do do Do. V y o Methy1 d do Scarlet.

Methyl--- do do do Red. [A

which are obtainable by the process des cribed in EX 150 parts of N.N-diphenyl-N.N-dihydroXyethyl-ethylenediamine are melted at 65. 131 parts of phenylisocyanate are dropped into the melt with stirring. After some time the reaction is completed. An excellent yield of the phenylcarbaminic acid ester of the N.N'-diph enyl- 8 Table 6 (III) (W) (v) Hydrogen Hydrogen. Scarlet.

d 0 Do.

Phcnyl Methoxy D0. 166.. Methy1 Me-i;hoxy D0. 167.. Methoxy d do Do. 168 Methyl. do D0. 169.. Methoxy Id Do. 170.. Methyl Methyl- Do. 171. Methoxy. d Do.

Formulae of representative tertiary amines of the foregoing examples are:

N.N-dihydroxyethyl-ethylenediamine is obtained. It is V coupled with 2-chloro-4-methyl-sulfonylbenzene-l-diazonium chloride to give a red powder which dissolves in acetone with an orange coloration. I

When the 150 parts of N.N'-diphenyl -N.N-d.ihydroxyethyl-ethylenediamine specified in the previous paragraph is replaced by 164 parts of N.N'-di-(3'-methyl)-phenyl- N.N'-dihydroXyethyl-ethylenediamine, another valuable tertiary amine is obtained. In this case; the product of coupling with 2-chloro-4-methylsulfonylbenzene-l-diazonium chloride is a red powder which dissolves in acetone with a red-orange'coloration.

Table 6 sets forth valuable water-insoluble tertiary amines of the formula.

They can be produced according to the directions given in Example 142 and are characterized by the symbols x, y, w and R in columns I to IV and by the shade in acetone solution of the coupling products with 2-chloro- 4-methylsulfonylbenzene-l-diazoniurn chloride in column EXAMPLE 1 O H,- G H;

EXAMPLE 2 CH7GH3 CHr-OHz-O-C O-NHQ' CH3 EXAMPLE 3 EXAMPLE 1 O 5 EXAMPLE 12s EXAMPLE 142 cm-cm-o-oo-mr-O Having thus disclosed the invention what is claimed is:

l. A water-insoluble tertiary amine which corresponds to the formula wherein x represents a member selected from the group consisting of a hydrogen atom, a halogen atom, a low molecular alkyl and a low molecular alkoxy radical,

y represents a member selected from the group consisting of a hydrogen atom, a halogen atom, a low molecular alkyl radical, a low molecular alkoxy radical, the trifluoromethyl radical, the trifiuoroacetyl radical and an alkanoylamino radical with not more than 18 carbon atoms,

n represents one of the integers l and 2,

R represents an alkylene radical with l to 4 carbon atoms,

R represents an alkylene radical with 2 to 4 carbon atoms,

R represents a member selected from the group consisting of a low molecular alkyl radical, a cycloalkyl radical, an unsubstituted phenyl radical, an alkylphenyl radical with from 1 to 5 carbon atoms in the alkyl group, a dimethylphenyl radical and a methoxyphenyl radical,

Z represents a member selected from the group consisting of an oxygen atom and an imino group, and

M represents a member selected from the group consisting of a hydrogen atom, a halogen atom, a low molecular alkoxy group, the cyano group, the difluoromethyl group, the trifluoromethyl group, a carbalkoxy group and the group when n has the value 1, and the single carbon-nitrogen linkage, when n has the value 2.

10 2. A water-insoluble tertiary amine which corresponds to the formula (o-CH|)l-|-H wherein R represents an alkylene radical with 2 to 4 carbon atoms, and each of m, n, and t is one of the integers l and 2.

3. The water-insoluble tertiary amine which corresponds to the formula 4. The water-insoluble tertiary amine which corresponds to the formula 5. The water-insoluble tertiary amine which corresponds to the formula 6. The water-insoluble tertiary amine which corresponds to the formula GE's-CH;

Zl l

7. The water-insoluble tertiary amine which corresponds to the formula 

1. A WATER-INSOLUBLE TERTIARY AMINE WHICH CORRESPONDS TO THE FORMULA 